1. Field of the Invention
The present invention relates to methods and systems for remediating contaminated water and soil, and, more particularly, to such methods and systems for decontaminating sites from organics and heavy metals.
2. Description of Related Art
Following a long period of environmental neglect, the United States and other countries have placed a high priority on remediating contaminated sites. It is estimated that between 300,000 and 400,000 contaminated sites are scheduled for cleanup in the United States in the coming decades, at an estimated cost as high as $500 billion to $1 trillion (National Research Council, "Alternatives for Ground Water Cleanup", Washington, D.C.: National Academy Press, 1994; M. Russell et al., Hazardous Waste Remediation: The Task Ahead, Knoxville: University of Tennessee, 1991). U.S. spending on waste site remediation totaled approximately $9 billion in 1996 alone.
Despite this considerable investment, conventional technologies for remediating contaminated sites, especially those with contaminated ground water, are inadequate. For example, the National Research Council has conducted a study of conventional ground water cleanup systems at 77 contaminated sites and determined that ground water cleanup goals had been achieved at only 8 of the sites and that full achievement was highly unlikely with the in-place technologies at 34 of the 77 sites (NRC, ibid., 1994; MacDonald and Kavanaugh, Envir. Sci. Tech. 28(8), 362A-68A, 1994). Based on these findings, it is believed that improved technologies are needed to restore contaminated sites.
The most common types of contaminants found at waste sites include chlorinated solvents, petroleum hydrocarbons, and metals (NRC, 1994). Chlorinated solvents, such as trichloroethane (TCE) and perchloroethylene (PCE), are used for such purposes as dry cleaning and degreasing industrial manufacturing equipment and cleaning military aircraft. Petroleum hydrocarbons commonly found in ground water include the components of gasoline, such as benzene, toluene, ethylbenzene, and xylene. Other common contaminants of ground water include naphthalene and chlorinated solvents. Because of the widespread use of both chlorinated solvents and petroleum hydrocarbons, contaminated ground water has been found in many sites around the world. Additional ground-water and soil contaminants comprise polycyclic aromatic hydrocarbons (PAHs), created from combustion, coal coking, and process, petroleum refining, and wood-treating operations; and polycholorinated biphenyls (PCBs), once widely used in electrical transformers and capacitors and for a variety of other industrial purposes.
Some conventional technologies for cleaning contaminated ground water are based on the principle that if enough water is pumped from the site, the contaminants will eventually be flushed out. In such "pump and treat" systems, the pumped-out water is treated ex situ to remove contamination, which has limited effectiveness, especially for cleaning up undissolved sources of contamination beneath the water table. Key contaminant and subsurface properties that interfere with flushing include: solubility of contaminants into water; diffusion of contaminant into micropores and zones with limited water mobility; absorption of contaminants to subsurface materials; and heterogeneity of the subsurface. Because of the difficulty of flushing contaminants from the subsurface, the NRC concluded in its 1994 study that pump and treat systems would likely be unable to restore fully many types of contaminated sites.
During the 1990s, as the limitations of conventional subsurface remedial technologies have become increasingly clear, new technologies have emerged to clean up contaminated soil and leaking underground storage tanks containing petroleum products. Some of these newer technologies used on contaminated ground water at U.S. Superfund sites include air sparging, bioremediation, passive treatment wall, dual-phase extraction, in situ well aeration, in situ oxidation, and pump and treat. Those used to clean up contaminated ground water at underground storage tanks include biosparging, dual-phase extraction, air sparging, in situ bioremediation, pump and treat, and intrinsic remediation. Air sparging, dual-phase extraction, pump and treat, passive treatment wall, and in situ well aeration technologies include high equipment and labor costs with mechanical treatment of ground water. Bio- and intrinsic remediation have exhibited a long-term approach but are largely unproven, primarily owing to problems associated with providing an environment optimal for multiplication of the microbes while consuming the contaminant(s).
Systems have been known in the art for oxidizing hydrocarbons to harmless chemical constituents. A strong oxidizing agent known for such a use is hydrogen peroxide. In a reaction known as the Fenton reaction, hydrogen peroxide can be mixed with a metallic salt such as ferrous sulfate to produce a free radical, which breaks bonds in the hydrocarbon molecule in an exothermic reaction to produce a low-free-energy state, generally comprising a production of carbon dioxide and water.
Particular in situ systems utilizing Fenton-type reactions have been disclosed by Brown (U.S. Pat. No. 4,591,443) and Wilson (U.S. Pat. No. 5,611,642), both of which include mixing the Fenton reactants prior to introduction into the soil and ground water. Vigneri (U.S. Pat. Nos. 5,286,141 and 5,520,483) has described a remediation method and system that includes a preacidification of the ground water prior to a sequential introduction of the Fenton reactants, wherein hydrogen peroxide is added after an injection of ferrous sulfate at a high concentration.